pplied K i n e t i c s q w ilib r ia 0.A. HOUGEN UNIVERSITY OF WISCONSIN, M A D I S O N , WIS.
T
without the ‘advantages ot intermediate pilot plant studies. This radical procedure was made possible by bold applications of fragmentary data on reaction rates combined Kith skillful application of the principles of dimensional similitude applied tc the phenomena of heat transmission, fluid flow,and diffusion, all of which occur concurrently in chemical reactions. I n June 1947, in Minneapolis, a t the annual ineetirlg oi the Americar, Society for Engineering Education, Garber ( 2 5 ) atrrssrd the importancc of training chemical engineers in the principles of reaction kind ics and presented a comprehen4w outline of a graduate courv in this fi~ld.
HE objective of this paper is to sunimarize the progresn which has been made from 1942 to date in developing and in applying the principles of chemical kinetics and equilibria such as are applicable directly to process design. A few references prior to 1942 are given to tie in the present status with the past. Significant areas are indicated R herein such principle& we lacking. This paper is .mitten primarily for the process engineer possessing a background in chemical engineering but without benefit of advanced training in statistical methods. The selection of papers for this review is a matter of persoiial choice, since there is no fixed demarcation between principles which belong t o scientific speculation and those which are dirrctly applicable to design. 1.
APPLIED KINETICS The typea of papers abstracted from the field of oi-ieixiical kinetics are those that report rate equations, reaction mcchanisms, methods of reactor design, and experimental data from which it may be possible to establish rate equations and other design information. This review passes by the more scientific achievements in theoretical kinetics and deals primarily witih the prosaic problems of reaction rate principles and data which are dirertly amenable to process design within the scope of graduate training offered in chemical engineering. The principles of kinetics should naturally be arranged aocording to phase relations and reaction mechanisms. I n this paper the applications to specific fields and the bibliography are arranged according to the classification of unit processes for the convenience of those engaged in specific chemical processes. HISTORICAL DEVELOPMENT
.
In the 1939 summer session lor teachers of chemical engineering held at Pennsylvania State College, Watson (47) stressed the importance of applied kinetics in the design of chemiral reactors
. and called attention to the lack of training and information avaiIable in this field. I n December 1942, in Chicago, the first Symposium on Applied Chemical Kinetics was held under the sponsorship of the AxmrCAN CHEMICAL SOCIETY ( 2 1 ) . I n soliciting papers for this symposium several hundred letters were sent to industrial chemists and chemical engineers engaged in process development. Only one paper from industry resulted from all this correspondence. This was typical of the status of applied chemical kinetics 6 years ago; either the information was not available or it was being held as stock in trade too valuable for release. Five years later a symposium on this same subject was sponsored by the American Institute of Chemcial Engineers in St. Louis, May 1947. This time nearly every request from industry met with favorable response. The attitude of chemical industries in releasing technical information on reaction rates had been altered by the experiences of production for war. Chemical industries had been forced by the necessity of building large plants for new processes, such as synthetic rubber production, to expand fragments of laboratory data directly into full scale chemical plants
DEVELOPMENTS IN THEORY
For 50 years laboratory studies in chemical kirieticii ha,ve bccn H popular pursuit. I n general, these studies have been made without the objective of application to process design, and usually were conducted under conditions which made extrapolation to manufacturing conditions difficult. I n the early gears not enough was known about chemical engineering principles t o make such applications successful. The literature on applied kinetics ia still meager and fragmentary. I n contrast, a n extensive and brilliant literature has been developed in theoretical kinetics. Through the tools of statistical and quantum mechanics a deep insight has been gained into the formation of activated complexes during chemical reactions; in the frequency of vibration and collision among molecules; in the relation of the thermodynamics to kinetics; in the surface contours of potential. energy during the oourse of a reaction; in calculation of bond energies to be broken and formed in molecular rearrangements; and in the theories of activated adsorption with and without dissociation in reactions catalyzed by solid surfaces. These theoretical speculations contributed by hundreds of scientists and culminating in the theory of absolute reaction rate first formulated by Eyring have been summarized in the classical text, “Theory of Rate Processes,” by Glasstone, Laidler, and Eyring ( 2 ) ~ Other significant books in the field of chemical kinetics, both theoretical and applied, are listed in the bibliography. Methods of applying chemical kinetics to process design may start with rate equations and reaction velocity constants without requiring deep exploration into the theoretical speculations that are involved in establishing a more rigorous approach. The process engineer accepts much of the theoretical background on faith. E A R L Y PAPERS ON APPLIED KINETICS
A few papers on applied kinetics prior to 1922 were written by Benton (14, 15) on the kinetics of catalyzed gas reactions in flow systems a t constant pressure; by Lewis and Ries (138) on the catalytic oxidation of sulfur dioxide; by MacMullin and Weber (40)on the theory of short circuiting in continuous flow mixing vessels in series and the Icinetics of chemical reactions in such systems; by Sherman (4.9) on the reaction rates of nonisothermal processes; and by Sherman, Quimby, and Sutherland (98)on the reaction between ethylene and the halogens and their
1556
September 1948
INDUSTRIAL AND ENGINEERING CHEMISTRY
products. Kinetics papers were written by McKee and Wilhelm (117) on the catalytic vapor phase nitration of benzene; by Bliss and Dodge (00) on the vapor phase hydration of ethylene t o ethanol; by Temlrin and Pyzhev (6.3) on the kinetics of the synthesis of ammonia on promoted iron catalysts; and by Lewis and Suen (116) on the rate of nitration of benzene. Pease contributed numerous kinetic papers including those on the polymerization of acetylene (155); on the noncatalytic polymerization and hydrogenation of ethylene (154); on the thermal chlorination of methane ( 9 7 ) ; on the hydrogenation of ethylene (103); on the dissociation of hydrocarbon vapors (78); with Echols (66) on the decomposition of n-butane; and with Morris (-96) on the thermal production of hydrogen chloride.
PROBLEMS ASSOCIATED W I T H KINETICS
A number of key problems needed to be solved before chemical kinetics could be applied to process design: the rate of transfer of heat and mass from a fluid stream to a solid catalyst; the diffusion of gases into catalyst pellets and solid reactants; the diffusion coefficient of gases in complex mixtures; and the pressure drop and thermal conductivity of fluid streams flowing through granular solids. Heat and mass transfer coefficients from gas streams to granular solids were obtained experimentally and evaluated for general use by Gamson, Thodos, and Hougen @4), by Hurt (M), and by Wilke and Hougen (50). Experiments with systems other than water and air are desirable t o verify the use of the present rate equations beyond the original experimental range. The theory of diffusion of reacting gases into porous solids was presented in a classical paper by Thiele (44), who introduced the terms “effectiveness factor” and “catalyst modulus.” This theory still awaits experimental verification and extension t o different reaction types. A simplified procedure of calculating the diffusion coefficients of gases in complex mixtures was presented by Hougen and Watson (4). D a t a .on pressure drop through granular beds were summarized by Oman and Watson (41) and more extensively by Leva (59), by Leva and Grummer (38), and by Brownell and Katz (18). A generalized method of correlating the viscosity of gases and liquids was developed by Uyehara and Watson (46). Methods of calculating the temperature gradients in reactors in both radial and axial directions were presented by Wilhelm, Johnson, and Acton (48). Later the method of Grossman (97) appeared and was extended by Hougen and Watson (4). A graphical method of calculating conversions and temperatures in nonisothermal reactions at constant volume is given by Greene, Sutherland, and Sklar (96). Data on the thermal conductivity of gas streams flowing through granular solids and on the transfer of heat from such fluid streams to reactor .walls have not been published. For nonflow systems extensive data are tabulated by Wilhelm, Johnson, Wynkoop, and Collier (49). The undesirable effect of channeling in reducing the degree of conversion in a commercial catalytic reactor was demonstrated by Berg, Fawcett, and Dhondt (16) in the operation of a hydroformer. RECENT DEVELOPMENTS IN APPLIED KINETICS
A significant series of papers on the application of chemical kinetics t o process design in complex systems was published recently by Wfttson and associates (54, 58, 76, 81-85). For the most part these.papers were published in the Technical Section of National Petroleum News and for that reason have not received wide circulation outside of the petroleum industry. The first paper with Reiser (58) dealt with the pyrolytic dealkyla-
1557
tion of aromatics, particularly with the conversion of xylene t o toluene and benzene and with the application of the data to the design of a tubular reactor by a stepwise procedure. In a second paper with Myers (76) the literature data on the pyrolysis of propane were analyzed with the securement of kinetic data 011 ten simultaneous reactions. These data were applied to the design of a tubular reactor for the pyrolysis of 1000 barrels per day of liquid propane with a conversion of 85% a t a maximum temperature of 1400” F. With Dodd (82, 83) preliminary data were secured on the catalytic dehydrogenation of n-butane and with Johanson (54) the catalytic production of toluene from benzene and xylene by methyl group transfer was investigated where the reaction rates were affected seriously by fouling of the catalyst with carhonaceous deposits. A fifth paper in this series was prepared with Beckberger (81) on the dehydrogenation of butene in the formation of butadiene. Other papers dealing with reactor design are by Burton, Chiswell, and Claussen (61)for the production of toluene from a narrow boiling petroleum fraction, and by Wenner and Dybdal (88) for the catalytic dehydrogenation of ethylbenzene. In the series of papers by Watson and associates a number of concepts were introduced into the literature which had been in use previously in process design divisions of the petroleum industry. Product distribution is defined as the moles of each product formed per mole of the key reactant; selectivity represents the percentage ratio of the moles of the desired product formed per mole of the converted key reactant t o the moles of desired product formed if there were no undesired reaction; equivalent reactor volume refers t o the volume of reactor actually required under the existing temperature schedule to the volume required a t a given reference temperature; and severity factor is that reactor volume a t unit pressure and at the selected reference temperature which is equivalent to the actual reactor volume per unit molal feed rate. Experimentally many data have been secured in constant volume nonflow reactors with negligible gradients of temperature, pressure, and concentration and with relatively large surface effects, whereas most industrial reactions proceed under flow conditions with large temperature, pressure, and concentration gradients and with small surface effects. The translation of experimental data from the first set of conditions to the second often is not possible and at best requires unusual skill in the application of dimensional analysis to the problems of fluid flow and heat tragsfer. In this connection it has been shown that the concept of ‘(time of contact” or “residence time” is of little practical value in flow reactions and can be replaced by the concept of reciprocal space velocity to great advantage. I n flow reactions in the steady state it is customary and advantageous to set up the rate equations without any reference to contact or residence time. The reciprocal space velocity of a fluid flowing through a reactor is a simple and easily measurable quantity, whereas residence time, particularly in gas flow, is an involve& concept which depends on temperature and pressure gradients, on changes in number of moles due t o the reaction, on phase distribution, and on the effective void fraction of the bed. These relations are presented by Brinkley (17).* Rate data may be obtained by either differential or integral reactors. Differential reactors are suited for the study of single reactions where a highly precise method for analysis of composition change is available. The advantage of the differential reactor is that it permits measurements of accurate values of average conditions within the reactor with respect to all variables in terms of the corresponding reaction rate. Integral reactors are necessary where large composition changes are required for accuracy of measurements, and are advantageous in studying complex changes where several reactions proceed simultaneously. T o study wide ranges in composition, many more runs are required in using an integral reactor than with a differential reactor in establishing the desired rate equations.
INDUSTRIAL A N D ENGINEERING CHEMISTRY
1558 H O M O G E N E O U S REACTIONS
Denbigh (go) presents an extensive discussion of the mathematics of reactions in flow systemq, and Hill ($9) discusses the :solution of differential equations which arise in the case of consecutive reactions. Hulburt, (34., 36) present,s two advanced papers on the theory of flow processes. Integrated equations for flow and nonflow syst,einsfor reversible and irreversible reactions of simple orders have been developed and summarized by IXougen and Watson (4). The method of securing kinetic data. on a. complex process with several simulhneous reactions for the decomposition of diphenyl is described in the same work. Striking examples of untangling complex kinetic data in homogeneous syst,ems are given by Myers and Watson (76) for the pyrolysis of propane where ten reactions proceed simultaneously. The same d a h are used in the design of a tubular reactor. For chain reactions in homogeneous systems Pease (9) reports his interpretation of the data of Bodenstein and Lind (103) in the formation of hydrogen bromine. The same analysis is extended to include the thermodynamic data of the sphtern and for the reverse reaction (4). iliethods of reactor design for complex homogeneous reactions h) stepwise procedures involving temperature and pressure gradients have been solved by Myers and Watson (76) in the pyrolysis of propane; by Reises and Watson (58) for the dealkylat,ion of xylene; and by Hougen and Watson (4)for the thermal decomposition of benzene into diphenyl and triphenyl. The combustion of gases is the most prevalent and least, understood of all homogeneous reactions. The classical treatment of this subject is presented by Lewis and von Elbe ( 7 ) . An international symposium on combustion, flame, and explosion phenomena is scheduled this summer in Madison, Wis., under the sponsorship of the University of Wisconsin. I n liquid systems, the most' extensive recent paper on the mechanism and kinetics of organic reactions is given in the T r a n s a c t i o n s of the F a r a d a y Society (45) I
CATALYTIC REACTIONS
The concepts of activated adsorption and chemisorption on active sites of a solid catalyst, combined with molecular dissociation and surface reactions are discussed extensively b j Glasstone, Laidler, and Eyring (2j. On the assumption that in a given suigle chemical reaction only one chemical step is rate controlling, Hougen and Watson ($9)developed thB rate equations for most of the posaible rate controlling mechanisms, such as activated desorption, adsorption n ith dissociation, impact of reactants with absorbed reaciants, and surface reactions on single bites or betneen adjacent sites. These equations include the equilibrium constants tor activated adsorption, for thc reverse reaction, and for the formation of the activated compleu. [ntegrated equations \\we developed for a few simple cabes (4). By observing the exchange of hydrogen and deuterium atoms, Hansford ( 7 4 ) explains the mechanism of catalytic crarlcing of hydrocarbons a5 due to the acceptance of protons from ?he hydrocarbon by water on a silica-alumina catalyst. The use of a cairiex gay in pioinoting reaction and in controlling temperature is illustrated b i r Mavity (8&-86) in the use of benzenc as a carrier gas in the dchyJrogenation of ethylbenzene. Steam is used in many systemq f o r the same purpose. The effect of fouling of the catalyst on reaction rates and method of dealing with deactivation in rate equations were shown by Reiser and Watson (68)in thc deallrylation of xylene, and by Johanson and Watson (64)in the production of toluene from benzene and xylene. Methods of evaluating the rate and equilibrium constants from the expwimental data of integral reactors me presented by Watson and a w ~ c i r t t e s(61, 58, 76) and for differential reactors by Tschernitz, Bornstein, Beckmann, and Hougen (104). Tn the latter papcr the method of selecting the
Yol. 40, No. 9
most plausible mechanism of a single reaction is demonstrated wherein one was selected from a list of seventeen postul~~ted mechanisms. It has been shown (104) that the effects of temperature on surface reaction velocity constants and equilibrium adsorption constants are conflicting; an increase in temperature increases the surface reaction velocity constant and decreases the adsorption equilibrium constant, both as experimental functions of temperature. For this reason the rate of a catalytic reaction may decrease with an increase in temperature even though the reverse reaction is negligible. The statement that reactions increase rapidly with increase in temperature does not apply categorically t o catalytic reactions. CLASSIFICATION OF CATALYTIC REACTlONS
A desirable objective in applied kinetics would be to classify reactions catalyzed by solid surfaces into the various chemical mechanisins which control the reaction. A few examples follow: Surface reactions v, ithoui dissociation: hydrogenation of isooctene (104); formation of toluene from benzene and xylene (64); and dehydrogenation of n-butane (82?83). Surface reactions with dissociation: oxidation of sulfur dioxide (139); activated adsorp-cion of one reactant; and synthesis of ammonia (61). Mass transfer in the gaseous phase 1s a controlling step in extremely rapid gas-solid reactions or gaseous reactions catalyzed by solid surfaces where the surface reaction is extremely rapid, such as in the combustion of lump coke (4) at high temperatures or oxidation of sulfur dioxide at high temperatures in the abjence of sulfur trioxide ( 4 ) . Mass transfer in the liquid phase is a rate controlling step where t h e contact reaction is extremely rapid such as in vapor phase esterification where a condensed phase form? on the catalyst (89). EMPIRICAL M E T H O D S
Several empirical ineLhods have been proposed for dealing with complex reactions. For catalytic reactions where mass transfer i s an important controlling rate Hurt (56) proposed the height of reactor unit concept with the use of the height of transfer unit for the gas film combined with a height of catalytic unit to account empirically for the rate controlling effect of the surface reaction The assumption of a pseudo fiist order reaction as a short-cut method has proved satisfactory for many complex hydrocarbon reactions, and methods for rapidly obtaining the pseudo reactiora velocity constants from experimental conversion data from graphs were developed by Johanson and Watson (64). U N C A T A L Y Z E D HETEROGENEOUS REACTlONS
Data on the kinetics of uncatalyzed heterogeneous reactions are scarce and the mechanisms only pa,rtly formulated (4). I n liquid-liquid reactions Lewis and Suen ( 1 1 6 ) have presented rate data, for the nitration of benzene by mixed acids and McKinley and White 118) give similar information on the nitration oE toluene by mixed acids. An extension of these treatments with the use of activity coefficients was developed later (4). The effect of agitation in promoting equilibrium distribution of reactants by mass transfer and turbulence in the two phases of a liquid-liquid reactor is expressed by the term contactor efficiency. Equations for contsctor efficiency for each liquid phase have been developed (4) Gas-solid reactions include the most important of all industrial reactions-namely, the combustion of solid fuels. Most elaborate and efficient designs far the combustion of solid fuels have been developed through experience by empirical methods. The kinetics of combustion have been too little understood to be applied successfully to furnace design. It has'been demonstrated ( 4 ) that mass transfer is a controlling step in the combustion of coke on a grate a t high temperatures where the initial mecha.nisrn ~
September 1948
INDUSTRIAL AND ENGINEERING CHEMISTRY
involves the transfer of oxygen to the surface of the hot coke with equilibrium formation of carbon monoxide at the solid surface. An example is given where the rate of combustion of coke is predicted from the experiments of mass transfer obtained in the evaporation of water from pellets by air a t low temperature (4). Reaction rates in metallurgical processes are fragmentary. In liquid-solid reactions data on the rate of dissolving crystals by liquids are scanty. Rate equations have been formulated by d u Domaine, Swain, and Hougen (106) on the softening of water by a granular cation exchanger and applied to the transient changes taking place in a fixed bed with respect t o time and position as water flows through the bed. Marshall and Hougen (33)have extended the theory for adsorption of gases in stationary granular beds and have presented charts for calculating the timeposition concentration of adsorbate gas for the special case’ where the isothermal equilibrium adsorption is linear with concentration. By extension of the method of Grossman (27) the general case of adsorption is presented by a tedious double stepwise procedure (SS). AMMONIA SYNTHESIS
Emmett and Kummer (61)have published the rate equations for the synthesis of ammonia on doubly promoted iron catalysts with evidence that the activated adsorption of nitrogen on the catalyst is the rate controlling step. Their experimental work and conclusions are in agreement with those of Temkin and Pyzhev (63). Equations for calculating the reaction rates and yields in flow systems are applied by Denbigh (60) to the synthesis of ammonia. Love and Emmett (69) presented the kinetics for the decomposition of ammonia by various catalysts. SUMMARY
I n general, industrial reactions are extremely complex not only with respect to the kinetics involved but also with respect to all the simultaneous and concomitant effects of heat conduction, mass transfer, turbulence, mixing, phase relations, and radiation: The application of kinetics accordingly is an undertaking which is unique and different for nearly every industrial reaction. A great deal of skill, experience, and ingenuity are required in any successful combination of all these principles to reactor design. In undergraduate instruction the separate principles should be presented but comprehensive problems involving the complexities of simultaneous reactions combined with the physical and thermal effects must be postponed for graduate studies and even then restricted to a few cases. Successful progress will be delayed also until machine methods are available for carrying out intricate and tedious calculations, thus freeing the mind for more profitable speculations.
BIBLIOGRAPHY ON APPLIED KINETICS BOOKS
(1) Daniels, Farrington, “Chemical Kinetics,” Ithaca, N. Y., Cornel1 University Press, 1938. (2) Glasstone, Laidler, and Eyring, “Theory of Rate Processes,” New York, McGraw-Hill Book Co., 1941. (3) Hinshelwood, C. N., “The Kinetics of Chemical Change,” New York, Clarendon Press, 1940. (4) Hougen, 0.A.,and Watson, K. M., “Chemical Process Principles,” Part 111, “Kinetics and Catalysis,” New York, John Wiley & Sons, 1947. (5) Jost, W., “Explosion and Combustion Processes,” New York, McGraw-Hill Book Co., 1946. (6) Kasiiel, L. S., “Kinetics of Homogeneous Gas Reactions,” New York, Chemical Catalog Co., 1932. (7) Lewis, B., and von Elbe, G., “Combustion, Flames, and Explosion of Gases,” London, Cambridge Univ. Press, 1938. (8) Moelwyn-Hughes, E. R., “The Kinetics of Reactions in Sohtion,” New York, Clarendon Press, 1933. (9) Pease, R. N., “Equilibrium and Kinetics of Gas Reactions,” Princeton, N. J., Princeton Uoiv. Press, 1942. (10) Rollefson, G. K.,and Burton, M., “Photochemistry and the Mechanism of Chemical Reactions,” New York, PrenticeHall (1939).
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(11) Bchum&cher,H. J., “Chemische Gasreaktionen,” Dresden and Leipzig, Steinkopff, 1938. (12) Schwab, A. M., Taylor, H. S., and Spence, R.,“Catalysis,” New York, D. Van Nostrand Co., 1937. (13) Semenov, N., “Chemical Kinetics and Chain Reactions,’’ New York, London, Oxford Univ. Press, 1935. GENERAL THEORY
(14) Benton, A. I?., IND. ENG.CHEM.,19,494(1927). (15) Benton, A. B., J . Am. Chem. SOC.,53,2984(1931). (16) Berg, C., Fawcett, P. N., and Dhondt, R. O., Chem. E n g . Progress, 43, 719 (1947). (17) Brinkley, S.R.,IND.ENG.CHEM.,40,303 (1948). (18) Brownell, L. E., and Kats, D. L., Chem. Eng. Progress, 43,537, 601,703 (1947). (19) Daniels, Farrington, IND.ENG.CHEM.,35, 504 (1943). (20) Denbigh, K.G., Trans. Faraday SOC.,50,352(1944). (21) Division of Industrial and Engineering Chemistry, AM. CKEM. SOC.,IND.ENG.CHEM.,35,501-80,617-700(1943). (22) Elkin, P. B.,Shull, C. G., and Roess, L. C., IND. ENG.CKEM., 37,327 (1945). (23) Eyring, Henry, Hulbert, H. M., and Harman, R. A,, Ibid., 35, 511 (1943). (24) Gamson, B. W., Thodos, G., and Hougen, 0. A., Trans. Am. I n s t . Chem. Engrs., 39,1 (1943). (25) Garber, H. J., Trans. Am. SOC.Eng. Education, Chemical Engr. Div. special papers, p. 47 (1947). (26) Greene, J. W.,Sutherland, J. B., and Sklar, G., IND.ENG. CKEM.,34,65 (1942). (27) Grossman, L. M., Trans. Am. Inst. Chem. Engrs., 42, 535 (1946). (28) Henriques, H. J., IND. ENG.CHEM.,39,1564 (1947). (29) Hill, T.L.,J . Am. Chem. SOC.,64,645 (1942). (30) Hirsch, J. H., Crawford, C. L., and Holloway, C., IND.EN*. CHEM.,38,885(1946). (31) Hirschfelder, J. O.,J. Chem. Phys., 9,645(1941). (32) Hougen, 0.A., and Watson, K. M., IND. ENG.CHEM.,35,529 (1943). (33) Hougen, 0.A,, and Marshall, W. R., Jr., Chem. Eng. Progress, 43, 197 (1947). (34) Hulburt, H.M., IND. ENG.CKEM.,36,1012 (1944). (35) Ibid., 37, 1063 (1945). (36) Hurt, D.M., Ibid., 35, 532 (1943). (37) Kassel, L. S.,Ibid., 31,275 (1935). (38) Leva, Max, and Grummer, M., Chem. Eng. Progress, 43, 549, 633,713 (1947). (39) Leva, Max, IND. ENG.CHEM.,39,857 (1947). (40) MacMullin, R. B., and Weber, M., Trans. Am. I n s t . Chem. Engrs., 31,409(1935). (41) Oman, 0.A., and Watson, X.M., Natl. Petroleum News, 36, No. 40,R795 (1944). (42) Ries, H. E., Van Nordstrand, R. A., and Tetev, J. W., IND. ENG.CHEM.,37,311 (1945). (43) Sherman, J.,Ibid., 28,1026 (1936). (44) Thiele, E.W., 31,916 (1939). (45) Trans. Faraday SOC.,37,601-806 (1941). (46) Uyehara, 0.A., and Watson, K. M., Natl. Petroleum N e w s , 36,No.40,R714 (1944). (47) Watson, K. M.,paper presented before summer session for
teachers of chemical engineering at Pennsylvania State College (1939). (48) Wilhelm, R. H., Johnson, W. C., and Acton, F. S., IND.ENQ. CHEM.,35, 562 (1943). (49) Wilhelm, R. H.,Johnson, W. C., Wynkoop, R., and Collier, D. W., Chem. &g. Progress, 44,105 (1948). (50) Wilke, C. R.,and Hougen, 0. A., Trans. Am. I n s t . Chem. Engrs., 41,445(1945). ALKYLATION
Burton, A. A., Chiswell, E. B., Claussen, W. H., Huey, C. S., and Senger, J. F., Chem. Eng. Progress, 44,195 (1948). Ciapetta, F. G., IND. ENG.CHEM.,37,1210 (1945). Gorin, M. H., Kuhn, C. S., and Miles, C. B., Ibid., 38, 795 (1946). (54) Johanson, L. N.,and Watson, K. M., Natl. Petroleum News, 38, No. 32, R629 (1946). (55) Linn, C. B., and Grosse, A. V., IND. ENG. CHDM.,37, 924 (1945). (56) Mattox, W.J., Trans. Am. Inst. Chem. Engrs., 41, 463 (1945). (57) Pardee, W. A., and Dodge, B. F., IND. ENG.CHEM.,35, 273 (1943). (58) Rei’ser, 6. O.,and Watson, K. M., Natl. Petroleum News, 38, No. 14,R260 (1946).
,
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 40, No. 9
HYDROGENATION
AMlN A T l O N
(59) Egly, R. S., and Smith, E. F., Chem. Eng.'Progress, 44, 387 (1948). AMMONIA SYNTHESIS
(60) Denbigh, K. G., Trans. Faraday Soc., 50, 352 (1944) (61) Emmett, P. H., and Kummer, J. T., IN^. ENG.CHEM.,35, 677 (1943). (62) Love, K . S., and Emmett,.P. H., J. Am. Chem. SOC.,63, 3297 (1941). (63) Temkin, M., and Pyzhev, V., Acta Physicochim. U.R.S.S., 12 327 (1940). I
CRACKING
Bednars, C., Lunta, D. M., and Bland, li. E., Chena. Enu. P T O Q T e S S , 44, 293 (1948). Echols, L. S., and Pease, R . N., J . Am. Chem. Soc., 61, 208 (1939). I b i d . , p. 1024. Good, G. M., Voge, H. H., and Greensfelder, B. S., I v n . CHEM.,39, 1032 (1947). Greensfelder, B. S , and Voge, H. H , lbirl., 37, 514 (1945). Ibid., p. 983. I b i d . , p. 1038. Ibid., p. 1168. Greensfelder, B. S., Voye, H. H., and Good, G , M . , Ihid., 38, 1033 (1946). Haensel, V., and Ipatieff. V N., Ibid., 35, 632 (1943). Hansford, R . C., Ibid., 39, 849 (1947). Kon-arewsky, V. I., and Watson, L., Ibid., 37, 323 (1945). Myers, P. S., and Watson, K. XI., Natl. Petroleum News, 38, N o . 18, R388 (1946). IMurphree, E. V., Brown, C. L., Gohr, E. J., Jahnig, C . E. Martin, H. Z., and T j s o n , C. W., Trans. A m . Inst. C'hrm Engrs.,41, 19 (1945). Pease, R. N., J . A m . Chem. SOC., 55, 3190 (1933). Thomas, C . L., I X D . E N G . CHCM.,37, 543 (1945). Vooi hies, rl.,Ibid., 37, 31 8 (1945). DEHYDROGENATION
(81) Reckberger, L. H., and Watson, K. M., Chem. Eng. P r o g r e s ~ 44, 229 (1948). ( 8 2 ) Dodd, R . H., and Watson, K. M., YTatZ. Petroleum N P - u )38, ~, No. 27, R545 (1946). (83) Dodd, R.H., and Watson, K . M., Trans. Am. Tnst. C h ~ m Enors. 42 263 (1946). (84) M a i i i y , J. M.Jand Zetterholm, E. IT., Tbid., 40,473 (1944). (85) Ibid., 41, 519 (1945). (86) Mavitv. J. 31..Zetterholm. E. E.. and Horvor. G . L.. 111, E N G . cHEhZ.,'38,829 (1946). (87) Russell, R. P., Muiphree, E . V., and Asbury, W. C., Trans. Am. Inst. Chem. EnQrS., 42, 1 (1946). (88) Wenner, R R., and Dybdal, E C., Chpm. En(/.P m Q r e w , 44, 193 (1948). \
,
(100) Anderson, N. K., and Rowe, C . h.,IND. h v ~ CHEM., . 35, 554 (1943). Beckmann, R. R., Pufahl, A E , and Hougen, 0. A , Ihid., 35, (101) 558 (1943). (102) Bodenstein, h l . , and Lind, S. C., 2. physik. Chpm., 57, 168 (1907). (103) Pease, R. N.,J. Am. L'hem. Soc., 54, 1876 (1932). 1104) Tschernitz, J. L., Bornstein, S., Beckmann, R. B., a ~ i dHougen 0.A., Trans. A m . Tnst. Phew Engrp., 42,883 (1946). IONIC EXCHANGE
(105) Barrer, R. M., aiid Ibbitson, 1). A , , Trans. li'a,'uday Soc., 50, 206 (1944). (106) du Domaine, J., Swain, R. L., and Hougen, 0. A., IND.ENG. CHEM.,35, 546 (1943). SOMERIZATION
(107) Cheney, €I. A, and Raymond, C. L., Trans. Am. Inst. Chem. Engrs., 42, 595 (1946). (108) Hay, R. G., Montgomery, C. W., and Coull, J., IND.ESG. CHEW.,37, 335 (1945). (109) Longtin, B., and Randall, M., Ibid., 34, 292 (1942). (110) McAllister, S. H., Ross, W. E., Randlett, H . E., and Ca,rlaon, G. J., Trans. Am. Inst. Chem. Engrs., 42, 33 (1946). (111) Oblad, A. G., and Gorin, M. H., IND.ENG. CHmf., 38, 822 (1946). (112) Oblad, A. G., Messenger, 5. U., and Brown, H. T., Ibid., 39, 1462 (1947). (113) Perry, 8. F., T r a m . Am. I n s t . Chem. Envrs., 42, 639 (1946). (114) Swearinpen, V. E., Geclrler. R . D., a,nd Nysewander, C . W.. Ibid., 42, 573 (1.946). NITRATION
(115) Egloff, G., Alexander, hl., arid Van Arudell, 1'. M., Oil Cas J . , 41, NO. 23, 39-41, 44; KO.24, 49, 51 (1942). (116) Lewis, W. K., and Suen, T. J., IND.ENG.CIIEM.,32, 1095 (1940). (117) McKee, R. H., and Wilheliri, 1%. H., Ibid., 28, 662 (1936). (1 18) McKinley, C., and White, R . R . , Trans. Am. I n s t . Chern. E'ngra 40, 143 (1944). OXIDATION
Faith, W.L., IND. Est,. CHEM., 37, 438 (1945). Faith, W. L., and Hollins, E. J., Ibid., 36, 91 (1944) Goldfinger, G., Mark, €1. and Siggia, S.,Ibid., 35, 1083 (1943). Kobe, K . A., and Hosman. P. D , Ibid.,40, 397 (1948). McBee, E. T., Hads, H. E., and Wiseman, P. A . , Ibid., 37, 4:32 (1945). (124) Michels, L. R., and Keyes, U. B., Ibid., 34, 138 (1942). (125) Shreve, R. N., and Welborn, R. W., Ibid., 35, 279 (1943). (126) Trans. Faraday Soc., 42,99-398 (1946).
(119) (120) (121) (122) (123)
POLYMERIZATION ESTERlFlCATlON
(89) Hoerig, H. F.,Hariaon, D. K,, and Kowalke, 0. L , , LND. ~ L K c , . CHEM., 35, 575 (1943). (90) Levesque, C. L., and Craig, A. M., Ibid., 40, 97 (1948). (91) Leyes, C. E., and Othmer, D . F., Ibid., 37, 968 (1945). (92) Leycs, C. E., and Othmer, D. F., T r a m . A m . I m t . L'h~rn. Engrs., 41, 157 (1945). (93) Mack, D. E., and Shreve, K. N., IXD. K x ; . (:HEM., 34, 304 (1942). (94) dchlechter, N., Othmer. D . F., wid Marshall, S., I h i d . , 37, 900 (1945). HALOGENATION
(95) MacMullin, R. B., ('hem. Eny. P,.ogress, 44, 183 (19481. (96) Morris, J. C., and Pease, €3. N., J. A m . ('hem. Soc., 61, :+$)ti (1939). (97) Pease, R . N., and W'alz, A. T., Zbid., 53,3728 (1931). (98) Sherman, A., Quimby, 0. T.. and Sutherland, O., ,J. ( ' h e n . Phys., 4, 732 (I 936).
(127) Baxendale, J. H., Evans, M. G., and Kilham, J. K., Trans. Faraday SOC., 42, 668 (1946). (128) Denbigh, K. G., Ibid., 43, 645 (1947). (129) Doumani, T. F., Deering, R. I?., arid McKinnij, A. C . , INCI. EKG.CHEM.,39, 89 (1947). (130) Farkas, A., and Farkas, L., Ibid., 34, 716 (1942). (131) Gee, G., and Melville, H . W.,Trans. Faraday Soc., 40, 240 (1944). (132) Ginell, R., and Simha, R., J. Am. Chern. SOC.,65, 706 (1943) (133) Pease, R. N., Ibid., 51, 3470 (1929). (134) Ibid., 52,1158 (1930). (135) Vaughan, W. E., Ibid., 54, 3863 (1932). PYROLYSIS
(136) Butler, E. T., Mandcl, N., and Polanyi, M.,Trans. Faraday SOC.,41, 298 (1945). (137) Ratchford, W. P., and k'isher, C. H., IUD.EYG.CHP:M.. 37, 38;: (1945). SULFURIC A C I D P R O D U C T I O N
HYDRATION 199) Bliss, R.
H., and Dodge, B. F.,IND. R N a . CHB:M., 29, I 9 (1937)
(138) Lewis, W. K., and Ries, Id. D., IND. ENG.C H m f . , 19, 890 (1923). (139) Uyehara, 0. A . , and Watson. K. M..Zhid., 35 541 (1943).
September 1948
INDUSTRIAL A N D ENGINEERING CHEMISTRY
APPLIED KINETICS AND EQUILIBRIA II. CHEMICAL AND PHYSICAL EQUILIBRIA Unlike chemical kinetics, the principles of thermodynamics are definite and rigorous. Standard patterns have been set u p fo? the behavior of ideal gases, incompressible liquids and solids, and ideal solutions. The deviations from such standard behavior are determined experimentally for each substance or system and unique results are reported under equations of state for gases, expansion factors for solids and liquids, and activity coefficientsfor solutions. Attempts have been made to establish generalizations for departures from ideality and considerable sucress has been attained for gases and pure liquids in terms of reduced properties. Vapor-liquid equilibria data have been formulated for ideal solution behavior even for multicomponent systems and for nonideal solution behavior for binary systems where ideal gas behavior is encountered. For nonideal solution behavior in multicomponent systems vapor-liquid equilibria relations are still in an uncertain state. The principles and bibliography dealing with this report on chemical and physical equilibria are classified according to phase relations. I n the section on kinetics, the discussion and bibliography are also arranged according to a classification based upon unit processes. For general use there is no good reason nor advantage in arranging thermodynamic data according to this latter scheme. Again, most of the references are for the years following 1941. THERMODYNAMIC PROPERTIES AND
Pvr DATA
For establishing with accuracy the thermodynamic properties of gases evaluation of P V T data is a necessary experimental
f
requirement with subsequent establishment of empirical equations of state from the resultant data. The Beattie-Bridgman and the BenedicbWebb-Rubin (34, S5) equations are among the most important and useful. The constants in these equations of state are unique for each gas and for each gaseous mixture. Extensive thermodynamic data on specific hydrocarbons and methods of application are given by Sage, Lacey, and co-workers (51-58, 65-67, 90) and on Freon refrigerants by Benning and McHarness (64). Of particular interest are the recent publications on the thermodynamic properties of air a t low temperatures by Williams (loo),of sulfur dioxide by Rynning and Hurd (89), and of carbon dioxide by Sweigert, Weber, and Allen (97). Recently determined thermodynamic properties of many other specific compounds are referred to in the bibliography. The most significant contribution to thermodynamics in recent years is the monumental compilation of data entitled "Tables of Selected Chemical Thermodynamic Properties," prepared with the support of the Naval Research Laboratory of the LTnited States Navy and the h'ational Bureau of Standards (292). This compilation of over 500 pages appears under three series, arranged according to individual compounds. In series I are arranged the values of heats of formation, free energies of formation, absolute entropies, heat capacities, and logarithms of equilibrium constants of formation, all at 25 O C., and of heats of formation a t 0' K. I n series I1 are arranged the heats, temperatures, and entropies of transition, of fusion, and of vaporization at various pressures. I n series 111 are tabulated the heats of formation, free energies of form'ation, logarithms of the equilibrium constants of formation, free energy functions, enthalpy functions, absolute entropies, and heat capacities all a t regular tempera1lire intervals from 0" K. to high temperatures. These tables of selected values of thermodynamic properties are consistent internally in that all the known physical and thermodynamic relations existing among the properties in the several tables are satisfied by the tabulated values of these properties. This compilation also includes selected vhlues of the proper-
1561
ties of hydrocarbons aa sponsored by the American Petroleum Institute, Research Project 44, National Bureau of Standards, dated May 31, 1947, and includes tables of fundamental constants, conversion factors, useful equations, and molecular weights. I n these tables numerical values of thermodynamic properties are tabulated against temperature relative to 0 ' K. This method of presenting thermodynamic functions replaces the use of tedious and time-consuming empirical equations. G E N E R A L I Z E D M E T H O D S F O R GASES AND LIQUIDS
Where the constants in PVT equations are not available or where highest accuracy i s not needed, the P V T data have been correlated on the assumption that all pure gases behave similarly at the same reduced temperature and reduced pressure. The mathematical relations have been too complex to be represented by any convenient reduced equation of state, although attempts have been made by Maron and Turnbull (48). These methodfi are particularly valuable for mixtures where experimental data are usually lacking. Generalized compressibility factors have been established and presented graphically in terms of reduced temperature and rcduced pressure by Cope, Lewis, and Weber ( S 7 ) , by Brown, Souders, and Smith (S6), by Dodge (38), by Newton (60), and by Watson and Smith ( S I ) , in order of progressive development. From these charts numerous derived thermodynamic charts have been developed for expressing the effects of pressure at different temperatures upon departure from ideal gas behavior: for enthalpy by Dodge (88), by Newton (50),by WatsonandNelson (99), and by York and Weber (101); for entropy by Weber (7): for heat capacity by Watson and Smith (31); and for fugacity by Souders, Selheimer, and Brown ( 1 7 4 , by Holcomb and Brown (76),by Lewis and Luke (I49), by Newton (60)and by Gamson and Watson (11'7, 118). The same charts can be used for gaE mixtures by employing pseudo reduced properties based on pseudo critical properties, as suggested and defined by Kay (16),instead of using the true critical properties of the mixtures. Methods of predicting critical constants are given by Meissner and Redding ( $ I ) , by Gamson and Watson (ZIT), and by Kuratn and Katz (141). A method for reporting the behavior of liquids was devised by Watson (98), wherein a generalized expansion factor w is expressed graphically in terms of reduced temperature and reduced pressure. The same expansion factor applies to nearly all liquids and is related to the density of a specific liquid by the ratio of density t o the expansion factor, pl/wl, at a given temperature. and pressure. This ratio is a unique constant for each liquid and can be related directly to chemical structure and molecular weight (98). By application of thermodynamics combined with the expansion factor chart, Gamson and Watson (117, 118) have constructed additional charts for expressing the effect of pressure on the enthalpy, entropy, and heat capacity of liquids a t various temperatures. Generalized methods have been developed also for establishing the vapor pressure of liquids ( I l 7 ) and heats of vaporization (74,88) as a function of reduoed ten)perature. T H E R M O D Y N A M I C CHARTS FOR SPECIFIC C O M P O U N D S
By the use of generalized charts combined with heat capacity equations of the gas, vapor pressure data, and a single value of entropy, charts such as the Mollier diagram for a given substance can be constructed easily and rapidly (8). Charts and tables constructed by these approximate methods serve well in the absence of more nearly accurate data and as a most useful guide in constructing tho more precise charts and tables from exact equations of state when such are available.
,
1562
INDUSTRIAL A N D E N G I N E E R I N G C H E M I S T R Y
ACTIVITY COEFFIENTS A N D V A P O R - L I Q U I D EQUILIBRIA
In establishing equilibria relations for nonideal solutions the methods of calculating activity coefficients as developed by Lewis and Randall (6) and the standard rtates proposed by them are still the accepted procedures. Molecular and ionic coefficients for nonideal solutions for specific systems continue to be reported in the literature without much success or hope in establishing any simple general correlations. A statistical approach to the study of the activity coefficients in multicomponent systems has recently been presented by TT70hl (32). For binary systems the equations of Margules (18), of Scatchard and co-workers (186-169), and of van Laar (27, 28) have been shown t o be obtainable by applying simplifying assumptions to tho equations of Wohl. For binary systems Carhon and Colburn (109) have presented several methods of establishing activity coefficients from the properties of an azeotrope, from simple measurements of total pressures or boiling points of liquid mixtures covering a wide range of compositions, and from equilibrium distribution between two liquid phases. Whitc (178) presents a method for con elating vapor-liquid equilibria in complex nonideal sybtems. High pressure vapor-liquid equilibria have been evaluated for ideal solution behavior and for lack of ideal gas behavior for multicomponent systems. For such behavior Brown and coworkers (108, ZY4, 179, 180) introduced the vaporization ratios, K,‘ for each component as the ratio of the mole fraction y, in the vapor phase to the molc fraction 5%in the liquid phase, which in turn in ideal solutions is equal to the ratio of the fugacity of the liquid to the fugacity of the gas both a t the standard state corresponding to the pure component at the temperature and pressure of the system. As a standard state for the liquid phase, Gamson and Watson (119) took the liquid a t a hypothEtica1 incompresrible state at the temperature of thc system. On the basis of these principles vapotization constants of each component in a multicomponent ideal solution have becn established. General methods for calculating vapor-liquid equilibria in multicomponent systems for nonideal solutions have been sought for many years in petroleum technology, but the problem still remains elusive. General discussion on the applications of thermodynamics are given by Redlich and Kister ($4) on nonelectrolyte solutions, and by Sage and eo-workers ($5, 150, 161, 159-161, 165, 166) on multioomponent systems. Vapor-liquid equilibria for specific ternary systems are given by Driclramer and Bradford (115), by Benedict, Solomon, and Rubin (105), by Gerster, Mertes, and Colburn ( I d O ) , by Hunter and Brown (133), by McCrirdy and Kata (146),by McMillan and McDonald (147),by Schneider and Lynch ( 1 7 l ) ,by Schumacher and Hunt (172), and by York and Holmes (182). Special mention should be made of the extensive investigations on vapor-liquid equilibria by Brown and associates (108, 128, 189, 136, 179, 180), by Colburn and associates (109, 110, 130, l S 4 , 148), by Othmer and associates (168-157) by Griswold and associates (121-166) and by Scatchard and associates (167-169). I n multicomponent hydrocarbon systems data and principlee are presented by Brown (108), by Brown and White (279, 180), by Gamson and Watson (117, ll8), by Miller and Barlcy (149), and by Roland (164). The phenomena of retrograde condensation are disrussed by Kat2 and Kurata (136,141). An excellent bibliography on vapor-liquid equilibrium is given by Hadden (126). GAS-SOLID EaUlLlBRlA
The thermodynamic theory of gas adsorption on solids is presented by Jura and Harkins (193). Pickett (196) gives a modification of the Rrunauer-Emmett-Teller theory of multimolecular adsorption. Equations for multimolecular adsorption are reported by Emmett (189). The relation of constitution to sdsorption on silica gel was investigated by Gyani and Ganguly
VOl. 40, No. 8
(192). Reyerson and associates (196-199) have published recent data on the adsorption of various gases on silica gel. LIQUID-LIQUID EQUILIBRIA
Liquid-liquid cquilibria are of special importance in the operation of solvent extraction. The attached bibliography gives detailed references to recent work in this field. A general discussion of distribution in hydrocarbon solvent systems is given by Brown ($06)and by Othmer and Tobiaz (227). OTHER SYSTEMS
The bibliography also gives references to equilibria and activity coefficients in aqueous solutions, in gas-liquid, in liquid-solid, and in solid-solid systems.
ACKNOWLEDGMENT Credit is acknowledged to John C. Garver €or his work in assembling the references for this review. BIBLIOGRAPHY ON THERMODYNAMICS AND EQUILIBRIA BOOKS
(1) Dodge, B. F ~“Chemical , Engineering Thermodynamics,” New York, McGraw-Hill Book Co., 1944. ( 2 ) Glasstone, S., “Thermodynamics for Chemis$s,” New York, D. Van Nostrand Co., 1947. (3) Hougen, 0.A., and Watson, K. M., “Chemical Procebs Principles, Part 11, Thermodynamirs,” New York, John Wiley & Sons, 1947. (4) Keenan, J. H.,“Thermodynamics,” New York, John Wiley & Sons. 1941. (5) Lewis, G. N., and Randall, &I., “Thermodynamics and tho Free Energy of Chemioal Substances,” New York, McGrawHill Book Co., 1923. (6) MacDougall, F. H.,“Thermodynamics and Chemistry,” New York, John Wiley & Sons, 1939.
(7) Weber. H. C., “Thermodynamics for Chemical Engineerss9’ New York, John Wiley & Sons, 1939. (8) Wenner, R. R.,“Thermochemical Calculations,” New York, -McGram-€IillBook Go., 1941. (9) Zexnansky, & W., I. “Heat and Therm-odynamics,” New York hlcGraw-Hill Book Co., 1943. GENERAL ARTICLES
(10) Bancroft, 15‘. D., and Hubard, S. S., J. Am. Chem. Soc., 64,347 (1942). (11) Bartell, P. E., and Benner, F. C., J s Phys. Cham., 47, 847 (1943). (12) Dahl, L.A,, Ibid.,50,96 (1946). (13) Huggins, M. L.,J . Am. Chem. Soc., 64,1712(1942). (14) Huntington, R.L., Petroleum Refiner, 23,107 (1944). (15) Kay, 1%‘. B., IND. E m . CHEM.,28,1014 (1936). (16) Koch, H. A.,and Williams, V. C.. Chem. Eng. Progress, 43,623 (1947). (17) Lype, E. F., Phys. Rev., 69,652 (1946). (18) Margules, &I., Sitzber. Alcad. Wigs. Wien., Math. naturzu. Klasse, 11, 104,1243-78 (1895). (19) Maron, 9. €I., and Turnbull, D., IND. END.CHEJI.,34, 544 (1942). (20) Mayfield, F.D., Ibid., p. 843. (21) Meissner, H. P., and Redding, E. M., Ibid., p. 521. (22) Oldenburger, R., Phys. Rev., 70,433(1946). (23) Prigogine, I., J. phys. radium, 5,185 (1944). (24) Redlich, O.,and Kister, A. T., IND. ENCT. CHEM., 40,341 (1948). (25) Sage, B.H., and Olds, R. H., Zbid., 34,526 (1942) (26) Stokes, E. H., J. Am. Chem. SOC.,67,1686 (1945). (27) van Laar, J. J., 2.p h y s i k . Chem., 72,723(1910). (28) Zbid., 185,35 (1929). (29) Ward, H. F.H., Trans. Faraday Soc., 42,399(1946). (30) Watson, K.M., IND. ENG.CHEM., 35,398(1943). (31) Watson, K. M.,and Smith, R. L., Natl. Petroleum News, 28, NO. 27,29-30, 32,34-6 (1936). (32) Wohl, K.,Trans. Am.Inst. Chem. Engrs., 42,215-50(1946). (33) Ying Fu,Hansen, R. S., and Bartell, F. E., J . Phys. Chem., 52, 374 (1948)+
September 1948
INDUSTRIAL AND ENGINEERING CHEMISTRY
w r RELATIONS (34) Beattie, J. A., Ingersoll, H. G., and Steckmayer, W. H., J. Am. Chem. SOC.,64,548 (1942). (35) BenediCt,M., webb, G . w., and Rubin, L. c., J , Chtm. phys., 8, 334-5 (1940). (36) Brown, G. G,, Souders, M., and Smith, R. L., IND, ENG,CHEM., 24, 513 (1932). (37) J * Q'? w' H ' 7 and H. c., Ibid*?23, 887 (1931). (38) Dodge, B. F., Ibid., 24, 1353 (1932). (39) Edwards, A. E., and Roseveare, W. E., J . Am. Chem. Soc., 67, 2816 (1942). (40) ~ ~ lw. ~ A., cueliar, i ~ ~A. M., , and ~ ~ w. N., d bid., 69, ~ 1972 (1947). (41) Felsing, W. A,, and Watson, G. M., Ibid., 65,780 (1943). (42) Ibid., p. 1889. (43) Gornowski, E.J., Amick, E. H.. and Hixson, A. N., IND.ENG. CHEM.,39, 1348 (1947). (44) Haney, R. E. D., and Bliss, H., Ibid., 36, 986 (1944). (45) Hirsch, M., Ibid., 34, 174 (1942). (46) Joffe, J., Ibid., 39,837 (1947). (47) Kelso, E. A., and Felsing, W. A., Ibid., 34, 161 (1942). (48) Maron, 8. H., and Turnbull, D., J. Am. Chem. 80% 64, 2195 (1942). and H*9 IND* ENG* 37p 667 (49) Morgen* (1945). (50) Newton, R. H., Ibid., 27, 302 (1935). (51) Olds, R. H., Reamer, H. H., Sage, B. H., and Lacey, W. N., Ibid., 35, 922 (1943). (52) Ibid., 36, 282 (1944). (53) Olds, R. H., Sage, B. H., and Lacey, W. N., Ibid., 38, 301 (1946). (54) Reamer, H. H., Korpi, K. J., Sage, B. H., and Lacey, W. N., Ibid., 39, 206 (1947). (55) Reamer, H. H., Olds, R. H., Sage, B. H., and Lacey, W. N.. Ibid., 36, 88 (1944). (56) Ibid., p. 956. (57) Ibid., 37, 688 (1945). (58) Reamer, H. H., Sage, B. H., and Lacey, W. N., Ibid., 38, 986 (1946). (59) Vaughan, W. E., and Collins, F. C., Ibid., 34,885 (1942). J'
T H E R M O D Y N A M I C PROPERTIES
(60) Aston, J. G., Fink, H. K., Bestul, A. B., Pace, E. L., and Szasz, E. S., J.Am. Chem. Soc., 68,52 (1946). (66) Aston, J. G., and Ziemer, C. W., Ibid., p. 1405. (62) Barkelew, C. H., Valentine, J. L., and Hurd, C. O., Chem. Eng. Progress, 43, 25 (1947). (63) Beckett, C. W., and Pitzer, K. S., J . Am. Chem. Soc., 68, 2213 (1946). (64) Benning' A*F*' and McHarness9 R''*, IND* ENG. 312 912 (1939) : 32, 497, 698, 814, 975 (1940). (65) Budenhplzer, R. A., Butkin, D. F., Sage, B. H., and Lacey, W. N., Ibid., 34,878 (1942). (66) Budenholzer, R. A,, Sage, B. H., and Lacey, W. N., Ibid., 35, 1214 (1943). (67) Corcoran, W. H., Bowles, R. R., Sage, B. H., and Lacey, W. N., 35, 1214 (1943). (68) Dousl*nv D' R**and Huffman*H. J * Am* Chem' SOc'p 68* 1704 (1946). (69) Edmister, W. C., IND. ENG.CHEM.,30, 352 (1938). (70) Egloff, G., andKuder, R. C., Ibid., 34,372 (1942). (71) Fischel, F. B., Naylor, B. F., Ziemer, c. W., Pmks, G. 8.9 and Aston, J. G., J. Am. Chem. Soc., 67, 2075 (1945). (72) Forsythe, W. R., and Giauque, W. F., Zbid., 64,48 (1942). (73) Gilliland, E. R., and Parekh, M. D., IND.ENQ.CIIEM., 34, 360 (1942). (74) Gordon, D. H., Ibid., 35,851 (1943). (75) Hanson, G. H., Trans. Am. Inst., Chem. Engrs., 42,959 (1946). (76) HolCombt D- E., and Brown, G- G., I N D . ENC.CHE% 34, 590 (1942). (77) Johnston, W. H., Bezman, I. I., and Hood, C. B., J. Am. Chem. Soo., 68, 2367 (1946). (78) Kilpatrick, J. E., and Pitaer, K. S., Ibid., p. 1066. (79) McCurdy, J. L., and McKinley, C., IND. ENG.CHEM.,34,1002 (1942). (80) Maron, S. H., and Turnbull, D., J. Am. Chem. SOC.,64, 44 (1942). (81) Matthews, C. S., and Hurd, C. O., Trans. Am. I n s t . Chem. Engrs., 42, 55 (1946). (82) Osborne, D. W., Doescher, R. N., and Yost, D. M., J. Am: Chem. SOC.,64, 169 (1942). (83) Pitzer, K. S., Guttman, L., and Westram, E. F., Ibid., 68,2209 (1946). M*l
1563
(84) Pitzer, K. S., and Scott, D. W., Ibid., 65,803 (1943). (85) Roebuck, J. R., Murre14 T. A., and Miller, E. E.,Ibid., 64, 400 (1942). (86) Rubin, T. R.9 Levedahl, €3. H.7 and Yost, D. Ma, Ibid.9 66, 279 (1944). H., Goldin& R*v., and Yost, D. M.t I b g v P. 16. (87) (88) Russell, H., Osborne, D. W., and Yost, D. M., Zbid., 64, 165 (1942). (89) Rynning, D. F., and Hurd, C. O., Trans, Am. Inst, Chem, Engrs., 41, 265 (1945). (90) Sage, B. H., and Lacey, W. N., IND.ENG. CHEM.?34, 730 (1942). (91) E. G., and Jenny, F.J., Ibid.9 37,990 (1945). ~ SCheibel, , (92) Schumann, S. C., Aston, J. G., and Sagenkahn, M., J. Am. Chem. SOC.,64, 1039 (1942). (93) Simon, J. H., and Smith, R. K., J.Phys. Chem., 46, 380 (1942). (94) Southard, J. C., and Moore, G. E., J . Am. Chem. SOC.,64, 1769 (1942). (95) Steams, W. V., and George, E. J., IND.ENG.CHEM.,35, 602 (1943). (96) Stevenin, T. G., and Allen, J. G., Ibid., p. 788. (97) Sweigert, R. L., Weber, P., and Allen, R. L., Ibid., 38, 185 (1946). (98) Watson, K, bid., 23,360 (1931); 35,398 (1943). (99) Watson, K. M., and Nelson, E. F., Ibid., 25,880 (1933). (100) Williams, V. S., Trans. Am. Inst. Chem. Engrs., 39, 93 (1943). (101) York, R., and Weber, H. C., IND. ENG.CHEM.,32, 388 (1940). (102) York, R., and White, E. F., Trans. Am. Inst. Chem. Engrs., 40, 227 (1944). VAPOR-LIQUID EQUILIBRIA
1
(lo3) J - PhVs. Chem*l 260 (1946)* (104) Beebe, A. H., Jr., Coulter, K. E., Lindsay, R. A,, and Baker, E. M., IND. ENG.CHEM.,34, 1501 (1942). (105) Benedict, M., Solomon, E., and Rubin, L. C., Ibid., 37, 55 (1945). (106) Blom, R. H., and Efron, A., Ibid.,p. 1237. (lo7) Mustakas* G * c.*Efront A.9 and Reed, Re L.1 Ibid., p. 870. (108) Brown, G. G., Petroleum Engr., 11,8,25,55 (1940). (109) Carlson, H. C., and Colburn, A. P., IND. ENG.CHEM.,34, 58 (1944). (110) Colburn, A. P., Schoenborn, E. M., and Shilling, D., Ibid., 35, 1250 (1943). (111) Conner, A. Z., Elving, P. J., and Steingiser, S., Ibid., 40, 497 (1948). B1oml
~ ~ ~ ~ a ~ , , s ~ ~ d , ~ ~ ~
(1944). (lI4) Drickamer' G'* Brown' G' G'T and R' R'f Trans' Am. Inst. Chem. Engrs., 41,555 (1945). (115) Dryden, C. E., IND. ENG.CHEM.,35,492 (1943). (116) Fritzche, R. H., and Stockton, D. L., Ibid., 38,737 (1946). (117) Gamson, B. W., and Watson, K. M., NatZ. Petroleum News, 36, No. 18, R258 (1944). (118) Ibid., No. 3, R554. (119) Ibid., N ~ 36, . R623. (120) Gerster, J. A., Mertes, T. S.,and Colburn, A. P., IND.ENO. CHEM.,39, 797 (1947). (121) Griswold, J., Ibid., 35,247 (1943). (122) Griswold, J., Andres, D., and Klein, V. A., Trans. Am. I n s t . Chem. Engrs., 37, 223 (1943). (123) Griswold, J., and Dinwiddie, J. A., IND. ENG.CHEM.,34, 1188 (1942). (124) Griswold, J., Haney, J. D., and Klein, V. A., Ibid., 35, 701 (1943). (125) Griswold, J., and Ludwig, E. E., Ibid., p. 117. (126) Hadden, S.T., Chem. Eng. Progress, 44,37,135 (1948). (127) Hafslund, E. R., and Lovell, C. L., IND. ENG.CHEM.,38, 556 (1946). (128) Hanson, G. H., andBrown, G. G., Ibid., 37,821 (1945). (129) Hanson, G. H., Rzasa, M. J., and Brown, G. G., Ibid., p. 1216. (130) Harrison, J. M., and Berg, L., Ibid., 38,117 (1946). (131) Holdren R. F., and Hixon, R. M., Ibid., p. 1061. (132) Holloway, C., and Thurber, S. H., Zbid., 36,980 (1944). (133) Hunter, T. G., and Brown, T., Ibid., 39,1343 (1947). (134) Jones, C. A., Schoenborn, E. M., and Colburn, A. P., Ibid., 35, 666 (1943). (135) Katz, D. L., and Brown, G. G., Ibid., 25, 1373 (1933). (136) Katz, D. L., and Kurata, F., Ibid., 32,817 (1940). (137) Kay, W.B., Ibid., 30,459 (1938). (138) Ibid., 32, 353 (1940). (139) Ibid., 33, 590'(1941). (140) Keevil, N. B., J . Am. Chem. Soc., 64,841 (1942). (141) Kurata, F., and Kats, D. L.. Trans. Am. I n s t . Chem. Engrs., 38, 995 (1942).
INDUSTRIAL AND ENGINEERING CHEMISTRY Langdon, W. M., and Keyes, D. B., IND.ENC. CHEM.,34, 938 (1942).
Lewis, W. K., and Luke, C. D., Ibid., 25, 725 (1933). Litvinov, N. D., J . P h y s . Chem. (U.S.S.R.),14, 782 (1940). LMcCurdy, J. L., and Katz, D. L., IND. ENG.CHEM.,36, 674 (1944)
Vol. 40, No. 9
(200) Smith, R . P., J . Am. C h a m Soc., 68, 1163 (1946). (201) Weiser, H. B., Milligan, W. O., and Holmes, J., J . Phys. ChPrn 46, 586 (1942). (202) Weiser, H. B., Milligan, T V ~8,.a,nd Simpson, W. C., Ibid.. 4 7 , 1051 (1943).
~
McDonald, H. J., and McMillan, W. R., l b i d . , p. 1175. McMillan, W. R., and McDonald, H. J., J . P h y s . Chem., 49, 10 (1945).
Mertes, T. S., and Colhurn, A. P., IND.ENG.CHEM.,39, 787 (1947).
Miller, C. O., and Barley, R. C., Ibid., 36, 1018 (1944) Olds, R. H., Sage, B. H., and Lacey, W. N., Ibid., 34, 1008 ~
(1942).
Ibid., p. 1223. Othmer, D. F., Ibid., p. 1072. Othmer, D. F., Ibid., 36,669 (1944). Othmer, D. F.. andBenenati, R. F.,Ibid., 37, 299 (1945). Othmer, D. F., and Gilmont, R., Ibid., 36, 858 (1944). Othmer, D. F., and Savitt, S. A., Ibid., 40, 168 (1948). Othmer, D. F., Schlechter, N., and Kosaalka, W. A., Ibid., 37, 895 (1945).
Ottenweller, J. H., Holloway, C., and Weinrich, W., Ibid., 35, 207 (1943).
Reamer, H. H., Olds, R. H., Saw, B. H., and Lacey, TTT. N., Ibid., 34, 1526 (1942). Ibid., 35,790 (1943). Ibid., 36,381 (1944).
Reamer, H. H., Sage, B. H., arid Lacey, W. N., Ibid., 39, 77 (1947).
Richards, A. R., and Hargreaves, E., Ibid., 36, 805 (1944). Roland, C. H., Ibid., 37, 930 (1945). Sage, B. H., and Lacey, W. N.? Ibid., 30, 1296 (1938). Sage, B. H., Reamer, H. H., Olds, R. H., and Lacey, W . N., Ibid., 34, 1108 (1942).
Scatchard, G., Chem. Rev., 8,321 (1931). Scatchard, G., and Hamer, TV. J., J . Am. Chem. SOC.,57, 1805 (1935).
Scatchard, G., Wood, 8 . E., and Mochel, J. h l . , Ibid., 68, 1957 (1946).
ScheibeI, E. G., and Jenny, F. J., IND.EKG.CHEM.,37, 80 (1945).
Schneider, C. H., and Lynch, C. C., J . Am. Chem. SOC., 65,1063 (1943).
Schumacher, J. E., and Hunt, H., IXD.ENG.CHEM.,34, 701 (1942).
Snyder, H. B., and Gilbert, E. C., Ibid., p. 1519. Souders, M., Selheimer, C. W., and Brown, G. G., Ibid., 24, 517 (1932).
Stage, H., andBaunigarten, J. S., O e l u . Kohle, 40, 126 (1944). Treybal, R. E., IND. ENG.CHEM.,36, 875 (1944). van Klooster, H. S., and Douglas. W. -A., J. Phys. Chem., 49, 67 (194t3.
WhiteiR-k, Trans. Am. I n s t . Chrm. Eng,.s., 41, 539 (1945). White, R. R., and Brown, G. G., N a t l . Petroleum N e w s , No. 43, R374, No. 47, R432 (1942)
White, R. R.. and Brown, G. G., IND. ENG.CHEM.,34, 1162 (1942).
Wood, S. E., J . Am. Chern. SOC.,68, 1963 (1946). York, R., and Holmes, R. C., IND.ENG.CHEM.,34, 345 (1942).
LIQUID-LIQUID EQUILIBRIA
(203) Alherty, R. X., and Washburn, E. P., J. Phys. Chem., 49, ‘C (1945). (204) Berndt, R . N . , and Lynch, C . C., J. Am. Chem. Soc.. 66, 282 (1944). (205) Briggs, S.W., and Comings, E. W., IXD. ENG.CHEW,35, 411 (1943). (206) Brown, T. F., Ibid.,40, 103 (1948). (207) Campbell, A. N., J . A m . Chem. Soc., 67, 981 (1945). (208) Darwent., B., and Winkler, C . A,, .T. Phys. Chem., 47, 442 (1943). (209) Denzler, C. G., Tbid.,49, 358 (1945). I b i d . , 47, 164 (1943). (210) Eckfeldt, E. L., and Lucasse, W. W., (21 1) Frantik, K. O., and McDonald, H. J., (preprint) “A Thernwdynamic Study of the Tin-Silver System,” Trans. Electrnchem. Soc., 88 (1945). (212) Ibid.,“A Theirnodynamic Study of the Tin-Antimony Syatern, (213) Fuoso, R. >I., J . Am. Chem. Soc., 65, 78 (1943). (214) Reymann, E., Martin, R. J. L., an.d Mulcahy, M. F. R., . I . .Phys. Cham., 47, 473 (1943). (215) Laddha, G. S., and Bmit,h, J. M . , LND. ESG. CHEM.,40, 497 (1948). (216) Major, C. J., and Swenson, 0 . J., I b i d . , 38, 834 (1946). (217) Othmer, D. F., and Tobias, P. E., Ibid., 34, 690, 693, BW (1942). (218) Smith, J. C., J. P h y s . Chem., 46, 376 (1942). (219) Smith, J. C., and Drexel, R. E., IND.ENG.CHErrZ., 37, 601 (1945). (220) Treybal, R. E., Weber, L. U., and Daley, J. F., .Ibid., 38, 877 (1946). (221) Washburn, E. R., and Stranskov, C . V., J . P h y s . Chem., 48. 241 (1944). (222) Wood, S.E., and Austin, A. E.. J . A m . Chem. Soc., 67, 4H( (1945). (223) Wood, S. E., mid Brusie, J. P., Ibid., 65, 1891 (1943). (224) .Yanko, J. A,. Diske, A. E., and Hworks, F. (preprint) “Tl~ei modynamic Studies of Dilute Solutions in Molten R i n a y .411oy?,” T r a n s . Electroch,em,. Sor., 89 (1 946) ”
~
SOLID-SOLID EQUILIBRIA
(225) Baile>, C. W., Bright, J. K. arid Ja\yer, J J., J . A7r~ C h r m SOC.,67, 1184 (1945). ( 2 2 6 ) Birchenall, C. E., and Mehl, 1%.F.,Am. Inst. ;Ilinino M r 7 Engr., 14, No. 4, Tech. Pub 2168 (1947). (227) Ehret, W.I?., and Gurinsky, D. H., J . Am. C‘hem. Soc., 65, 11% (1943). (22s) Fink, H . L., Clines, M. R.. Erey, F. E., and -&aton, J. G., 1hi.i 69, 1501 (1947). (229) Holmes, E. O., and Retinson D., Ibid., 66, 453 (1944) (230) Musappar, S. D., and Chand, R., Ibid.,p. 1374. (231) Seltz, H., and Dunkerlev, F J.. Tbzd.,64, 1992 (1942)
GAS-SOLID EQUILIBRIA
LIQUID-SOLID EQUILIBRIA
(183) Armbruster, M. H., J.Am. Chem. Soc., 65, 1043 (1943). (184) Beebe, R. A., Beckwirth, ,J. B.,and Honig, J. M., Ibid., 67, 1554 (1945). (185) Brines, E., and Sguaetaniatti,Helv. Chim. Acta, 25,370 (1942). (186) Brunauer, S., Love, K . S., and Keennn, R. G., J . Am. Chsm. SOC., 64, 751 (1942). (187) Davis, R. T., Ibid., 68, 1305 (1946). (188) Docken, L. S., and Gurry, R. W., Ibid., 67, 1398 (1945) (189) Emmett, P. H., Ibid., 68, 1784 (1946). (190) Emmett, P. H., and Cines, M , Ibid., p. 2535. (191) Griffen, C. W . , I b i d . , 64, 2610 (1942). (192) Gyani, B. P., and Ganguly, P. B., J . Phgs. Chem., 49, 226 (1945). (193) Jura, G., and Harkins, W.D., J. Am. Chem. SOC.,68, 1941 (1946). (194) Pickett, G., Ibid.,67, 1958 (1945). (195) Poettman, F. H., and Kats, D. L., IND.ENQ.CHEM.,38, 530 (1946). (196) Reyerson, L. H., and Bemmels, C., J . Phys. Chem,., 46, 31 (1942). (197) Ibid., p.’35. (198) Reyerson, L. H., and Cines, M. It.,Ibid., 46, 1060 (1942). (199) Ihid., 47, I060 (1943).
(232) Everaole, W. G., and H a n s o n , - 3 . I,., J. P h y s . Chein., 47, I (1943). (233) Eversole, W. G., Hart, T. F., and Wapner, G. H., Ibid., p. 701 (234) Hudson, D. R., Ibid., 49, 483 (1945). (235) Lucazse, W.W.,Koob, P. P., and >Idler, J. G., I b i d . , 48, 85 (1944). 1236) Noble, M. Y , arid Gairetl, A B., J . ’4712 Chem. Soc., fi6, 2 3 ( I 944). GAS-LIQUID
(237) Darkin, L. S.,and G u n ? , I%, IV.?J. Am. Chem. Soe., 68, 7Yx (1946). (238) DaGdson, A. W.,Sisler, H . H., arid Stoeiincr, R., I b i d . , 66, 779 (1944). (239) Marshall, S , and Chjinin, J., 7’)arks A m SOC.Metals, 30, 693 (1942). (240) h-elson, E. E., and Bonnell, M’. S., IND. ENG.C H E W35, , 80% (1943). (241) Othmer, D. F.. and White, R.E., Ibid.,34, 952 (1942). (242) Poettman, F. H.. and Kats, D. L., Ibid.,37, 847 (1946). (243) Riegger, E., Tartar, H. V., and I , i n g a f e l t r r , F C , J A m . (Vi, t f C SOC, 66, 2024 (1444).
September 1948
INDUSTRIAL AND ENGINEERING CHEMISTRY
THERMODYNAMICS OF AQUEOUS SOLUTIONS
Ayres, F. D., J . Phvs. Chem., 49,366 (1945). Bates, R. G., J . Am. Chem. Soc., 64, 1136 (1942). Bayliss, N. S., Cole, A. R. H., Ewers, W. E., and Jones, N. X., Ibid., 69, 2033 (1947).
Bogardus, H. F., and Lynch, C . C . , J . Phys. Chem., 47, 660 (1943).
Broene, H. H., and DeVries, T., J . Am. Chem. SOC.,69, i644 (1947).
Brosheer, J. C., and Anderson, J. F., Ibid., 68,902 (1946). Brown, E. H., Cline, J. E., Felger, M. M., and Howard, R. B., IND. ENG.CREM.,ANAL.ED.,17,280 (1945). Crockford, H. D., and Wideman, S. A,, J . Phys. Chem., 50,418 (1946)
I
Ehret, W. F., and Frere, F. J., J . Am. Chem. SOC.,67, 68 (1945). Ervin, G., Giorgi, A. L., and McCarthy, C. E., Ibid., 66, 384 (1944).
Eversole, W. G., and Hart, T. F., J . Phys. Chem., 46, 555 (1942).
Fajans, K., and Johnson, O., J. Am. Chem. Soc., 64,668 (1942). Furukawa, H., and King, G. B., J.Phys. Chem., 48, 174 (1944). Garrett, A. B., Bryant, R., and Kieffer, G. F., J . Am. Chem. SOC.,65, 1905 (1943). Gee, E. A., Ibid:, 67, 179 (1945). Green, S. J., and Frattali, F. J., Ibid., 68, 1789 (1946). Hornibrook, W. J., Janz, G. J., and Gordon, A. R., Ibid., 64, 513 (1942). Janz, G. J., and Gordon, A. R., Ibid., 65,218 (1943). Jones, F. E., J . Phys. Chem., 48, 311, 356, 379 (1944). Jones, J. H., and Fuming, H. R., J . Am. Chem. Soc., 66, 1672 (1944). Jones, J. H., and Heckman, N., Ibid., 69, 536 (1947). Jones, J. H., Spuhler, F. J., and Felsing, W. A., Ibid., 64, 965 (1942). Lightfoot, W. J., and Prutton, C. F., Ibid., 68, 1001 (1946). Ibid., 69, 2098 (1947). Mason, C . M., and Blum, W. M., Ibid., p. 1246. Miles, G. L., Ibid., p. 1716.
1565
(270) Mowen, R. A., and Walker, R. D., IND.ENQ.CHEIM.. 37. 1186 (1945). (271) Phjllips, B. A., Watson, G. M., and Felsing, W. A., J . A m Chem. Soc., 64, 244 (1942). (272) Ricci, J. E., Ibid., 66, 1015 (1944). (273) Ricci, J. E., and Aleshnioh, J. J., Ibid., p. 980. (274) Ricci, J. E., and Linke, W. F., Ibid., 69, 1080 (1947). (275) Ricci, J. E., and Nesse, G. J., Ibid., 64, 2805 (1942). (276) Ricci, J. E., and Smiley, 8. H., Ibid., J . Am. Chem. SOC.,66, 1011 (1944). (277) Robinson, R. A., Trans. Faraday Soc., 41,756 (1945). (278) Robinson, R. A., Wilson, J. M., and Ayling, H. S., J . Am. Chem. SOC.,67, 1469 (1942). (279) Soatchard, G., and Prentiss, S. S., Ibid., 56,1486 (1934). (280) Schultz, J. F., and Elmore, G. V., IND. ENG.CHEM.,38, 296 (1946). (281) Simons, E. L., and Ricci, J. E., J . Am. Chem. SOC.,68, 1413 (1946). (282) Simons, E. L., and Ricci, J. E., Ibid., p. 2194. (283) Smith, S. B., Ibid., 69, 2285 (1947). (284) Stokes, J. M., Trans. Faraday Soo., 41, 686 (1945). (285) Stokes, R. H., Ibid., p. 12. (286) Ibid., p. 637. (287) Stokes, R. H., and Levien, B. J., J. Am. Chem. SOC.,68, 333 (1946). (288) Ibid.. D. 1852. (289) Stokes’, R. H., Stokes, J. M., and Robinson, R. A., T r a n s Furud a y Soc., 40, 533 (1944). (290) Temkin, M., Acta Physicochim., U.R.S.S., 20,411 (1945). (291) Van Hook, A., and Shields, D., IND.ENQ. CHEW, 36, 1048 (1944). GENERAL TABLES
(292) Natl. Bureau of Standards, Dept. of Commerce, “Tables of Selected Chemical Thermodynamic Properties,” March 31, 1947. RECEIVED April 23, 1948.
ALKYLATION E R. NORRIS SHREVE PURDUE UNIVERSITY, LAFAYETTE, IND.
I
N THE past few years much work has been done on the fundamental chemistry connected with alkylation and its application to industry. This review presents alkylation by the method of bonding the alkyl group into the rest of the molecule under the following heads: alkyl bonded t o oxygen, alkyl bonded to nitrogen (both tertiary and quaternary), alkyl bonded to carbon, and alkyl bonded t o other elements (principally metals). Industrially much of the alkylation work that has been applied t)o our factories during the past few years has been in the petroleum field or in the preparation of ethylbenzene for the manufacture of styrene t o enter into synthetic rubber. Both of these latter alkylations fall within the classifications of carbon to carbon bonds. I n large tonnages the pioducts of these reactions were employed in the war effort. Around 175,000 tons of styrene were made in 1944 and 1945 out of ethylbenzene, and many times this amount of alkylate were made for aviation gasoline. In any unit process, there are both the basic chemical factors of kinetics, equilibria, catalysis, etc., and the industrial features of equipment, economics, flow charts, and the like. I n this review a few general articles are separated and arranged under. the heading of physicochemical considerations, but most of the chemical as well as the technical aspects are reviewed where the article in question is arranged in the general classification according to the type of bonding, This review covers 1941 through 1947 and a very few important
articles appearing in the first few months of 1948. It includes in the literature cited most of the general articles but only a small proportion of the patents. If all had been included, the number of references would probably have approached a thousand. However, when available, references arh given to extensive patent compilations (119). As the outstanding development during this period that falls within the unit process of alkylation is the study and commercialization on a large scale of the manufacture of alkylate for high octane motor fuel, this subject is reviewed and presented in more detail than any other.
PHYSICOCHEMICAL CONSIDERATIONS The mechanism of the alkylation of isobutane with olefins catalyzed by acids and aluminum halides is explained by Gorin, Kuhn, and Miles (66) with supporting experimental evidence. This mechanism consists in the addition of methyl and isopropyl fragments from isobutane t o form an olefin-catalyst complex. Ciapetta (3.9)explains the alkylation of isoparaffins through the carbonium ion mechanism (see also 166). Extensive experiments were conducted by Linn and Grosse (88) on the alkylation of several isoparaffins by olefins in the presence of hydrofluoric acid in both batch and flow processes, with studies on the effects of temperature, feed composition, and concentration of hydrofluoric acid. A number of general studies on the fundamentals of alkylation in the petroleum field have been published-e.g., Egloff and Hulla (41) review the alkylation of alkanes and Caesar
